TWI593631B - Apparatus for preparing germane gas and method for preparing monogermane gas using the same - Google Patents
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Description
本發明關於一種鍺烷氣體製備裝置及利用其製備單鍺烷氣體之方法。本發明特別關於一種鍺烷氣體製備裝置,藉由在短時間之內混合起始原料,有能力穩定地產生大量單鍺烷氣體,並且使用具有微結構通道之一反應器同時移除反應熱,及利用其製備單鍺烷氣體之方法。 The present invention relates to a decane gas producing apparatus and a method of producing a monodecane gas using the same. More particularly, the present invention relates to a decane gas producing apparatus capable of stably producing a large amount of monooxane gas by mixing a starting material in a short time, and using a reactor having a microstructured passage to simultaneously remove the heat of reaction, And a method of using the same to prepare a monodecane gas.
鍺烷氣體(Germane gas)被使用於半導體產業中,其使得應變矽(strained silicon)得以應用於電腦中央處理器中,且已成為新興的鍺通道與閘極之關鍵材料。此外,鍺烷氣體被用於形成第五代非晶矽薄膜太陽能電池(a-Si太陽能電池)的三接面(Triple junction)的中間SiGe層,藉此增強對於中段波長範圍300-900nm光線之吸收以及改善電池之效率。據此,隨著對於下一代薄膜太陽能電池之需求量可預期的增加,對於鍺烷氣體之需求亦可望隨之快速成長。 Germane gas is used in the semiconductor industry, which enables strained silicon to be used in computer central processing units and has become a key material for emerging germanium channels and gates. In addition, decane gas is used to form an intermediate SiGe layer of a triple junction of a fifth-generation amorphous germanium thin film solar cell (a-Si solar cell), thereby enhancing light for a medium wavelength range of 300-900 nm. Absorb and improve the efficiency of the battery. Accordingly, as the demand for next-generation thin-film solar cells is expected to increase, the demand for decane gas is expected to grow rapidly.
自1930年代以來,許多化學家研究鍺烷氣體的合成以及其所牽涉的化學反應。典型的例子包含,一種化學方法使用硼氫化鈉(NaBH 4)、鋁氫化鋰(LiAlH 4)等化合物還原二氧化鍺(GeO 2)或 四氯化鍺(GeCl 4),一種電化學方法電解二氧化鍺,以及一種高能方法直接將鍺(Ge)與氫氣反應。 Since the 1930s, many chemists have studied the synthesis of decane gas and the chemical reactions involved. Typical examples include a chemical method of reducing cerium oxide (GeO 2 ) using a compound such as sodium borohydride (NaBH 4 ) or lithium aluminum hydride (LiAlH 4 ) or Neodymium tetrachloride (GeCl 4 ), an electrochemical method for the oxidation of cerium oxide, and a high energy method directly react cerium (Ge) with hydrogen.
至於以現行方法使用二氧化鍺或四氯化鍺製備鍺烷氣體,其產率大約僅有70%。尤其,當使用相較於四氯化鍺更容易處理之二氧化鍺製備單鍺烷氣體時,難以在高產率下製備單鍺烷氣體。 As for the preparation of decane gas using ceria or ruthenium tetrachloride in the current method, the yield is only about 70%. In particular, when a monodecane gas is produced using cerium oxide which is easier to handle than ruthenium tetrachloride, it is difficult to prepare a monodecane gas at a high yield.
有鑑於此,美國專利第4,668,502號揭示,即便使用相同之二氧化鍺作為原料,藉由調整反應條件,即二氧化鍺之濃度、溶解二氧化鍺之鹼性水溶液中鹼/二氧化鍺之比例、鹼金屬硼氫化物之量、酸的濃度、反應溫度等之組合,鍺烷氣體之產率可增加至高達97%。確實,當依照美國專利第4,668,502號實施例與申請專利範圍中所指定之反應條件進行實驗時,可達成約90%的高鍺烷產率。 In view of the above, U.S. Patent No. 4,668,502 discloses the use of the same cerium oxide as a raw material by adjusting the reaction conditions, i.e., the concentration of cerium oxide, and the ratio of alkali/cerium oxide in an aqueous alkaline solution in which cerium oxide is dissolved. The combination of the amount of alkali metal borohydride, the concentration of the acid, the reaction temperature, and the like, the yield of the decane gas can be increased up to 97%. Indeed, when tested in accordance with the reaction conditions specified in the examples of U.S. Patent No. 4,668,502 and the scope of the patent application, about 90% of the high decane yield can be achieved.
然而,若根據上述方法,將該溶解二氧化鍺及鹼金屬硼氫化物之鹼性水溶液與該酸性水溶液以批次或連續的反應,鍺烷氣體會在短時間內爆炸性的產生,並伴隨著高反應熱。這代表,若以工業規模而非實驗室規模進行鍺烷氣體之製備,反應速率與反應熱將會難以控制。假若高反應熱並未被適當控制,反應溫度將會快速上升(約50℃或更高),以及可能生成較高的鍺烷,因此對於單鍺烷之產率具有負面的影響。 However, according to the above method, the alkaline aqueous solution of the dissolved ceria and the alkali metal borohydride is reacted with the acidic aqueous solution in batch or continuously, and the decane gas is explosively generated in a short time, accompanied by High reaction heat. This means that if the preparation of decane gas is carried out on an industrial scale rather than on a laboratory scale, the reaction rate and heat of reaction will be difficult to control. If the high heat of reaction is not properly controlled, the reaction temperature will rise rapidly (about 50 ° C or higher), and higher decane may be formed, thus having a negative effect on the yield of monodecane.
本發明之發明人付出了持續的努力來解決上述問題。結果,發現了該問題可藉由在短時間之內混合起始原料,並且使用具有微結構通道之一反應器同時移除反應熱而得到解決。 The inventors of the present invention have made continuous efforts to solve the above problems. As a result, it was found that the problem can be solved by mixing the starting materials in a short time and using a reactor having one of the microstructure channels while removing the heat of reaction.
合成氣態鍺烷之方法(Method of synthesis of gaseous germane,US 4,668,502) Method of synthesis of gaseous decane Germane, US 4,668,502)
鍺烷之生產方法(Production method of germane,JPA 1998-291804) Production method of germane (Production method of germane, JPA 1998-291804)
本發明係關於一種鍺烷氣體製備裝置,以及利用其製備單鍺烷氣體之方法,特別關於一種鍺烷氣體製備裝置,藉由在短時間之內混合起始原料,並使用具有微結構通道之一反應器有效率的同時移除反應熱,藉此控制鍺烷氣體產生時快速增加之溫度與壓力,有能力穩定地生產大量單鍺烷氣體,以及利用其製備單鍺烷氣體之方法。 The present invention relates to a decane gas producing apparatus, and a method for producing a monodecane gas therewith, and more particularly to a decane gas producing apparatus by mixing a starting material in a short time and using a microstructured passage A reactor efficiently removes the heat of reaction while controlling the rapidly increasing temperature and pressure at which the decane gas is generated, has the ability to stably produce a large amount of monodecane gas, and a method of preparing a monodecane gas therefrom.
於一通常的態樣,本發明提供了一種單鍺烷氣體製備方法,包含:分別於一第一通道及一第二通道中,注入一包含二氧化鍺(GeO 2)與鹼金屬氫化物之起始原料鹼性水溶液及一酸性水溶液;於一連接該第一通道之一端與該第二通道之一端的第三通道中,混合該注入之起始原料鹼性水溶液及酸性水溶液,並使其反應以產生單鍺烷氣體與一反應溶液;以及,將該產生之單鍺烷氣體與該反應溶液排放至該第三通道之外,其中,該第三通道中所產生之反應熱,藉由於鄰近該第三通道配置之一冷卻劑循環單元中循環之一冷卻劑加以吸收。 In a general aspect, the present invention provides a method for preparing a monodecane gas, comprising: implanting a cerium oxide (GeO 2 ) and an alkali metal hydride in a first channel and a second channel, respectively; a starting material alkaline aqueous solution and an acidic aqueous solution; mixing the injected starting material alkaline aqueous solution and the acidic aqueous solution in a third channel connecting one end of the first channel and one end of the second channel, and Reacting to produce a monodecane gas and a reaction solution; and discharging the produced monodecane gas and the reaction solution to the outside of the third channel, wherein the reaction heat generated in the third channel is caused by One of the coolants circulating in the coolant circulation unit adjacent to the third channel configuration is absorbed.
在一示例性實施例中,該第三通道可為一微通道。 In an exemplary embodiment, the third channel can be a microchannel.
在一示例性實施例中,該第三通道可包含一主要通道以及一構成於該主要通道一側之複數個平行突出的突出部分。較佳地,該複數個突出部分可對於該主要通道具有一銳角並且可朝一個方向突出。 In an exemplary embodiment, the third passage may include a main passage and a plurality of parallel protruding projections formed on one side of the main passage. Preferably, the plurality of protruding portions may have an acute angle to the main passage and may protrude in one direction.
在一示例性實施例中,該第三通道可被維持在0-50℃之溫度。 In an exemplary embodiment, the third channel can be maintained at a temperature of 0-50 °C.
在一示例性實施例中,該第三通道之溫度可藉由調控至少一選自冷卻劑之流量、冷卻劑之溫度以及該起始原料鹼性水溶液或該酸性水溶液之流速加以控制。 In an exemplary embodiment, the temperature of the third passage can be controlled by adjusting at least one flow selected from the group consisting of a coolant, a temperature of the coolant, and a flow rate of the starting aqueous alkaline solution or the acidic aqueous solution.
在一示例性實施例中,該第三通道中所產生之反應熱,可被傳導至包圍該第三通道之一第一金屬塊,該傳導至第一金屬塊之反應熱可被傳導至與該第一金屬塊接觸之一第二金屬塊,該傳導至第二金屬塊之反應熱可被傳導至被第二金屬塊包圍之一冷卻劑循環單元,以及該傳導至冷卻劑循環單元之反應熱可被於該冷卻劑循環單元中循環之一冷卻劑吸收。 In an exemplary embodiment, the heat of reaction generated in the third channel may be conducted to a first metal block surrounding one of the third channels, and the heat of reaction conducted to the first metal block may be conducted to The first metal block contacts one of the second metal blocks, and the heat of reaction conducted to the second metal block can be conducted to a coolant circulation unit surrounded by the second metal block, and the reaction to the coolant circulation unit Heat can be absorbed by one of the coolants circulating in the coolant circulation unit.
在一示例性實施例中,該第三通道之數量可至少為一,該至少為一之第三通道可被平行的連接,以及該起始原料鹼性水溶液與該酸性水溶液可被分別地注入該至少為一之第三通道之中,以便在該至少為一之第三通道產生單鍺烷氣體。 In an exemplary embodiment, the number of the third channels may be at least one, the at least one third channel may be connected in parallel, and the starting material alkaline aqueous solution and the acidic aqueous solution may be separately injected. The at least one of the third channels is configured to produce a monodecane gas in the at least one third channel.
在一示例性實施例中,該鹼金屬氫化物可為硼氫化鈉(NaBH 4)。 In an exemplary embodiment, the alkali metal hydride can be sodium borohydride (NaBH 4 ).
在一示例性實施例中,其中該酸性水溶液可包含一無機酸或一有機酸,其中該無機酸可為一或多個選自包含硫酸與磷酸組 成之群組,以及該有機酸可為一或多個選自包含醋酸與丙酸組成之群組。 In an exemplary embodiment, wherein the acidic aqueous solution may comprise an inorganic acid or an organic acid, wherein the inorganic acid may be one or more selected from the group consisting of sulfuric acid and phosphoric acid. The group, and the organic acid may be one or more selected from the group consisting of acetic acid and propionic acid.
於另一通常的態樣,本發明提供一種鍺烷氣體製備裝置,包含:供起始原料鹼性水溶液注入之一第一通道;供酸性水溶液注入之一第二通道;連接該第一通道與該第二通道之一端之一第三通道,且於其中混合與反應該起始原料鹼性水溶液與該酸性水溶液,以產生單鍺烷氣體與一反應溶液;供該第三通道中產生之單鍺烷氣體與該反應溶液透過其排放的一排放出口;以及一冷卻劑循環單元,其係鄰近該第三通道配置,以及一冷卻劑被注入進及排放出該冷卻劑循環單元,其中該第三通道所產生之反應熱被該冷卻劑吸收。 In another general aspect, the present invention provides a decane gas preparation apparatus comprising: a first channel for injecting an alkaline aqueous solution of a starting material; a second channel for injecting an acidic aqueous solution; and connecting the first channel with a third channel of one end of the second channel, wherein the alkaline aqueous solution of the starting material and the acidic aqueous solution are mixed and reacted to generate a monodecane gas and a reaction solution; for the single channel generated in the third channel a decane gas and a discharge outlet through which the reaction solution is discharged; and a coolant circulation unit disposed adjacent to the third passage, and a coolant injected into and discharged from the coolant circulation unit, wherein the first The heat of reaction generated by the three channels is absorbed by the coolant.
在一示例性實施例中,該第三通道可為一微通道。 In an exemplary embodiment, the third channel can be a microchannel.
在一示例性實施例中,該第三通道以及該冷卻劑循環單元可被彼此相隔的配置,該第三通道可被一第一金屬塊包圍,該冷卻劑循環單元可被一第二金屬塊包圍,以及該第一金屬塊與該第二金屬塊可被彼此接觸的配置。 In an exemplary embodiment, the third passage and the coolant circulation unit may be disposed apart from each other, the third passage may be surrounded by a first metal block, and the coolant circulation unit may be a second metal block Enclosing, and a configuration in which the first metal block and the second metal block are contactable with each other.
根據本發明,鍺烷氣體產生時快速增加之溫度與壓力,可藉由在短時間之內混合起始原料,並使用具有微結構通道之一反應器可有效率的同時移除反應熱並加以控制。以及,根據本發明,單鍺烷氣體可被大量且高產率的生產。 According to the present invention, the rapidly increasing temperature and pressure of the decane gas can be obtained by mixing the starting materials in a short period of time and using a reactor having a microstructured passage to efficiently remove the heat of reaction and control. And, according to the present invention, monodecane gas can be produced in a large amount and in high yield.
1‧‧‧批次反應器 1‧‧‧ batch reactor
2‧‧‧循環器 2‧‧‧Circulator
3‧‧‧起始原料鹼性水溶液儲存器 3‧‧‧ starting material alkaline aqueous reservoir
4‧‧‧酸性水溶液儲存器 4‧‧‧Acid aqueous reservoir
5‧‧‧冷卻劑循環單元 5‧‧‧ coolant circulation unit
6‧‧‧計量泵 6‧‧‧Measuring pump
7‧‧‧記錄器 7‧‧‧ Recorder
8‧‧‧排放出口 8‧‧‧Emissions exports
10‧‧‧第一通道 10‧‧‧First Passage
20‧‧‧第二通道 20‧‧‧second channel
30‧‧‧第三通道 30‧‧‧ third channel
30a‧‧‧主要通道 30a‧‧‧ main channel
30b‧‧‧突出部分 30b‧‧‧ highlight
40‧‧‧排放出口 40‧‧‧Exhaust export
50‧‧‧冷卻劑循環單元 50‧‧‧ coolant circulation unit
55a‧‧‧冷卻劑入口 55a‧‧‧ coolant inlet
55b‧‧‧冷卻劑排放出口 55b‧‧‧ coolant discharge
60‧‧‧金屬塊 60‧‧‧metal blocks
60a‧‧‧第一金屬塊 60a‧‧‧First metal block
60b‧‧‧第二金屬塊 60b‧‧‧Second metal block
第1圖 係根據先前技術之批次(batch)反應器之一示 意圖。 Figure 1 is a representation of a batch reactor according to the prior art. intention.
第2a圖 係根據本發明一示例性實施例之鍺烷氣體製備裝置之一爆炸圖。 Fig. 2a is an exploded view of one of the decane gas producing devices according to an exemplary embodiment of the present invention.
第2b圖 係根據本發明一示例性實施例之鍺烷氣體製備裝置之一組裝圖。 Fig. 2b is an assembled view of a decane gas producing apparatus according to an exemplary embodiment of the present invention.
第3a圖 係根據本發明一示例性實施例之鍺烷氣體製備裝置中之第三通道之一示意圖。 Fig. 3a is a schematic view showing one of the third passages in the decane gas producing apparatus according to an exemplary embodiment of the present invention.
第3b圖 係根據本發明一示例性實施例之鍺烷氣體製備裝置中之第三通道之一放大圖。 Fig. 3b is an enlarged view of one of the third passages in the decane gas producing apparatus according to an exemplary embodiment of the present invention.
第4圖 表示實施例1-4中之第三通道之溫度變化。 Fig. 4 shows the temperature change of the third channel in the examples 1-4.
第5圖 表示實施例4與比較實施例1中之第三通道之溫度變化。 Fig. 5 shows changes in temperature of the third channel in Example 4 and Comparative Example 1.
在此,本發明將被詳細的描述。 Here, the present invention will be described in detail.
本發明所使用之術語「微通道(micro-channel)」指的是一微結構通道。該通道可具有範圍從數微米至數千微米之一直徑。 The term "micro-channel" as used in the present invention refers to a microstructured channel. The channel can have a diameter ranging from a few microns to a few thousand microns.
本發明所使用之術語「反應溶液」指的是起始原料鹼性水溶液與酸性水溶液反應產生鍺烷氣體之後殘存之溶液。 The term "reaction solution" as used in the present invention refers to a solution remaining after the alkaline aqueous solution of the starting material is reacted with an acidic aqueous solution to produce a decane gas.
根據本發明之一種鍺烷氣體製備裝置,包含:供起始原料鹼性水溶液注入之一第一通道10;供酸性水溶液注入之一第二通道20;連接於該第一通道10與該第二通道20之一端之一第三通道30,且於其中混合與反應該起始原料鹼性水溶液與該酸性水溶液, 以產生單鍺烷氣體與一反應溶液;一排放出口40,該第三通道中產生之單鍺烷氣體與該反應溶液透過該排放出口排放;以及一冷卻劑循環單元50,其係鄰近該第三通道30配置,以及一冷卻劑被注入進與排放出該冷卻劑循環單元50,其中該第三通道30所產生之反應熱被該冷卻劑吸收。具體而言,該第三通道30可為一微結構通道。具體而言,該第三通道30以及該冷卻劑循環單元50可被彼此間隔的配置,該第三通道30可被一第一金屬塊60a包圍,該冷卻劑循環單元50可被一第二金屬塊60b包圍,以及該第一金屬塊60a與該第二金屬塊60b可被彼此接觸的配置。 A decane gas producing apparatus according to the present invention, comprising: a first channel 10 for injecting an alkaline aqueous solution of a starting material; a second channel 20 for injecting an acidic aqueous solution; and connecting to the first channel 10 and the second a third channel 30 at one end of the channel 20, and mixing and reacting the starting material alkaline aqueous solution and the acidic aqueous solution therein, To generate a monodecane gas and a reaction solution; a discharge outlet 40, the monodecane gas generated in the third passage and the reaction solution are discharged through the discharge outlet; and a coolant circulation unit 50 adjacent to the first A three-channel 30 configuration, and a coolant are injected into and discharged from the coolant circulation unit 50, wherein the heat of reaction generated by the third passage 30 is absorbed by the coolant. Specifically, the third channel 30 can be a microstructure channel. Specifically, the third passage 30 and the coolant circulation unit 50 may be spaced apart from each other, the third passage 30 may be surrounded by a first metal block 60a, and the coolant circulation unit 50 may be a second metal The block 60b surrounds, and the first metal block 60a and the second metal block 60b are arranged to be in contact with each other.
該第一通道10,並不限定於特定態樣,只要該起始原料鹼性水溶液係注入其中,以及該注入之起始原料鹼性水溶液係傳輸至該第三通道30。具體而言,該第一通道10可具有一圓管之形狀。具體而言,該第一通道10可具有耐腐蝕性與耐酸性。該第一通道10可由一種或多種選自陶瓷、不鏽鋼、鈦金屬等材料製造。 The first channel 10 is not limited to a specific aspect as long as the starting material alkaline aqueous solution is injected therein, and the injected starting material alkaline aqueous solution is transported to the third channel 30. Specifically, the first passage 10 may have a shape of a circular tube. Specifically, the first passage 10 can have corrosion resistance and acid resistance. The first passage 10 can be made of one or more materials selected from the group consisting of ceramics, stainless steel, titanium metal, and the like.
該起始原料鹼性水溶液可藉由將二氧化鍺(GeO 2)與一鹼金屬氫化物以及一鹼性水溶液混合製備。該鹼金屬氫化物可為硼氫化鈉(NaBH 4)。製備該起始原料鹼性水溶液之方法,並不限定於特定態樣。舉例來說,該起始原料鹼性水溶液,如美國專利第4,668,502號中所描述,可藉由添加一鹼金屬氫化物粉末至二氧化鍺(GeO 2)之金屬氫氧化物水溶液中製備,或藉由預先製備一預定濃度之鹼性水溶液以及隨後於其中加入二氧化鍺粉末與鹼金屬氫化物製備。在本發明所使用之起始原料鹼性水溶液中,二氧化鍺之濃度具體而言可不高於0.5mol/L,更具體而言為0.3mol/L。具體而言,每1mol之二氧化鍺, 可包含2或更多當量的該金屬氫氧化物,以及每1mol之二氧化鍺,可包含4mol或更多的該鹼金屬氫化物。在上述範圍之外,可能降低二氧化鍺的轉換比率,以及因而降低單鍺烷氣體生產之經濟效益。該鹼性水溶液可為一鹼金屬水溶液或一鹼土金屬水溶液,具體而言為一NaOH水溶液或一KOH水溶液。若使用一NaOH水溶液以及若使用NaBH 4作為一鹼金屬氫化物製備該起始原料鹼性水溶液,因為NaBH 4被穩定化氫氣不會被產生。 The starting material alkaline aqueous solution can be prepared by mixing cerium oxide (GeO 2 ) with an alkali metal hydride and an alkaline aqueous solution. The alkali metal hydride can be sodium borohydride (NaBH 4 ). The method of preparing the alkaline aqueous solution of the starting material is not limited to a specific aspect. For example, the starting material alkaline aqueous solution, as described in U.S. Patent No. 4,668,502, may be prepared by adding an alkali metal hydride powder to a metal hydroxide aqueous solution of cerium oxide (GeO 2 ), or It is prepared by previously preparing a predetermined concentration of an aqueous alkaline solution and subsequently adding cerium oxide powder and an alkali metal hydride thereto. In the alkaline aqueous solution of the starting material used in the present invention, the concentration of cerium oxide may specifically be not more than 0.5 mol/L, more specifically 0.3 mol/L. Specifically, every 1 mol of cerium oxide, It may contain 2 or more equivalents of the metal hydroxide, and may contain 4 mol or more of the alkali metal hydride per 1 mol of cerium oxide. Outside of the above range, it is possible to reduce the conversion ratio of cerium oxide and thus the economic efficiency of monodecane gas production. The alkaline aqueous solution may be an aqueous alkali metal solution or an alkaline earth metal aqueous solution, specifically an aqueous NaOH solution or an aqueous KOH solution. If an aqueous solution of NaOH is used and if a basic aqueous solution of the starting material is prepared using NaBH 4 as an alkali metal hydride, hydrogen is not produced because NaBH 4 is stabilized.
該第二通道20,並不限定於特定態樣,只要該酸性水溶液係注入其中,以及該注入之酸性水溶液係傳輸至該第三通道30。具體而言,該第一通道10可具有一圓管之形狀。具體而言,該第二通道20可具有耐腐蝕性與耐酸性。該第二通道20可由一種或多種選自陶瓷、不鏽鋼、鈦金屬等材料製造。 The second passage 20 is not limited to a specific aspect as long as the acidic aqueous solution is injected therein, and the injected acidic aqueous solution is transported to the third passage 30. Specifically, the first passage 10 may have a shape of a circular tube. Specifically, the second passage 20 may have corrosion resistance and acid resistance. The second passage 20 may be made of one or more materials selected from the group consisting of ceramics, stainless steel, titanium metal, and the like.
該酸性水溶液可藉由選自無機酸(如,硫酸及磷酸等)或有機酸(如,醋酸及丙酸等)之一酸與水混合製備。具體而言,考慮到單鍺烷氣體之純化,可避免揮發酸(如,鹽酸)之使用。該酸性水溶液並不限定於特定濃度。 The acidic aqueous solution can be prepared by mixing an acid selected from a mineral acid (e.g., sulfuric acid and phosphoric acid) or an organic acid (e.g., acetic acid, propionic acid, etc.) with water. Specifically, the use of a volatile acid such as hydrochloric acid can be avoided in consideration of purification of a monodecane gas. The acidic aqueous solution is not limited to a specific concentration.
該第三通道30,並不限定於特定態樣,只要其係連接於該第一通道10之一端與該第二通道20之一端,以及該鹼性水溶液與該酸性水溶液於其中混和與反應。具體而言,該第三通道30可為一微結構通道。該微結構通道之直徑與長度,可依據該裝置之尺寸以及鍺烷氣體所需之生產量變換。具體而言,其可介於數十微米至數百微米之間。 The third channel 30 is not limited to a specific aspect as long as it is connected to one end of the first channel 10 and one end of the second channel 20, and the alkaline aqueous solution is mixed and reacted with the acidic aqueous solution. Specifically, the third channel 30 can be a microstructure channel. The diameter and length of the microstructure channel can vary depending on the size of the device and the throughput required for the decane gas. Specifically, it may be between several tens of microns and several hundred microns.
該第三通道30可包含一主要通道30a以及構成於該 主要通道一側之複數個平行突出的一突出部分30b。該複數個突出部分30b可對於該主要通道具有一銳角並且可朝一個方向突出。藉由包含該主要通道30a以及該突出部分30b,該第三通道30可以使通過其中之流體持續地向上與向下移動,以及使該流體得以被分離(split)或重組(recombine)。具有這種構造,該第三通道30不只可以使分別由該第一通道10與該第二通道20注入之起始原料水溶液與酸性水溶液輕易的混合,同時藉由該起始原料水溶液與該酸性水溶液接觸面積之增加,亦可促進鍺烷氣體之產生。該第三通道30可進一步包含一溫度感測器(未示出)。該溫度感測器可以對該第三通道30進行即時的溫度測量,藉此可輕易控制反應溫度與冷卻劑通過該冷卻劑循環單元50之流量,並藉此增加單鍺烷氣體之產率。 The third channel 30 can include a main channel 30a and is configured A plurality of protruding portions 30b projecting in parallel on one side of the main passage. The plurality of protruding portions 30b may have an acute angle to the main passage and may protrude in one direction. By including the main passage 30a and the protruding portion 30b, the third passage 30 can continuously move the fluid passing therethrough upward and downward, and the fluid can be split or recombined. With such a configuration, the third channel 30 can not only easily mix the aqueous starting material solution injected from the first channel 10 and the second channel 20 with the acidic aqueous solution, but also the aqueous solution of the starting material and the acid. The increase in the contact area of the aqueous solution also promotes the production of decane gas. The third channel 30 can further include a temperature sensor (not shown). The temperature sensor can perform an immediate temperature measurement of the third passage 30, whereby the reaction temperature and the flow rate of the coolant through the coolant circulation unit 50 can be easily controlled, thereby increasing the yield of the monodecane gas.
該排放出口40並不限於特定態樣,只要於該第三通道30產生之鍺烷氣體與反應溶液可被排放出該第三通道30。該排放出口40連接於該第三通道30之一端,以及具體而言,可具有一圓管之形狀。該連接於該第三通道30之一端之排放出口40的直徑,可依據該裝置之尺寸以及鍺烷氣體所需之生產量變換。 The discharge outlet 40 is not limited to a specific aspect as long as the decane gas and the reaction solution generated in the third passage 30 can be discharged out of the third passage 30. The discharge outlet 40 is coupled to one end of the third passage 30 and, in particular, may have the shape of a circular tube. The diameter of the discharge outlet 40 connected to one end of the third passage 30 can be varied depending on the size of the apparatus and the amount of production required for the decane gas.
該冷卻劑循環單元50可鄰近於該第三通道30配置。其包含供冷卻劑注入之一冷卻劑入口55a以及供冷卻劑排放之一冷卻劑排放出口55b。其並不限於特定態樣,只要吸收該第三通道30中產生之反應熱之冷卻劑可通過其中。該冷卻劑循環單元50可為可供冷卻劑通過的一線形或之字形管道。該冷卻劑循環單元50的直徑,可依據該裝置之尺寸以及鍺烷氣體所需之生產量變換。 The coolant circulation unit 50 can be disposed adjacent to the third passage 30. It contains a coolant inlet 55a for coolant injection and a coolant discharge outlet 55b for coolant discharge. It is not limited to a specific aspect as long as the coolant that absorbs the heat of reaction generated in the third passage 30 can pass therethrough. The coolant circulation unit 50 can be a linear or zig-shaped conduit through which the coolant can pass. The diameter of the coolant circulation unit 50 can be varied depending on the size of the apparatus and the amount of production required for the decane gas.
該於冷卻劑循環單元50中循環之冷卻劑並不限於特 定態樣,只要其係為可透過位於該冷卻劑循環單元50之一端之一冷卻劑入口55a注入與透過位於該冷卻劑循環單元50之另一端之一冷卻劑排放出口55b排放,以及不會在0℃或更低之溫度凝固。具體而言,其可為乙二醇(ethylene glycol)。 The coolant circulating in the coolant circulation unit 50 is not limited to a special one. The stationary state is as long as it is permeable to the coolant discharge inlet 55a located at one end of the coolant circulation unit 50 and is discharged through the coolant discharge outlet 55b located at the other end of the coolant circulation unit 50, and It solidifies at a temperature of 0 ° C or lower. Specifically, it may be ethylene glycol.
在一示例性實施例中,該第三通道30以及該冷卻劑循環單元50可被彼此相隔的配置,該第三通道可被一第一金屬塊60a包圍,該冷卻劑循環單元50可被一第二金屬塊60b包圍,以及該第一金屬塊60a與該第二金屬塊60b可被彼此接觸的配置。在該示例性實施例中,該第三通道30中所產生之反應熱被傳導至該包圍第三通道之第一金屬塊60a,傳導至該第一金屬塊60a之反應熱被傳導至該與第一金屬塊60a接觸之第二金屬塊60b,以及該傳導至該第二金屬塊60b之反應熱被傳導至該被第二金屬塊60b包圍之冷卻劑循環單元50。該傳導至冷卻劑循環單元50之反應熱被該於冷卻劑循環單元50中循環之冷卻劑吸收。 In an exemplary embodiment, the third passage 30 and the coolant circulation unit 50 may be disposed apart from each other, the third passage may be surrounded by a first metal block 60a, and the coolant circulation unit 50 may be The second metal block 60b surrounds, and the first metal block 60a and the second metal block 60b are disposed in contact with each other. In the exemplary embodiment, the heat of reaction generated in the third channel 30 is conducted to the first metal block 60a surrounding the third channel, and the heat of reaction conducted to the first metal block 60a is conducted to the The second metal block 60b that the first metal block 60a contacts, and the heat of reaction conducted to the second metal block 60b are conducted to the coolant circulation unit 50 surrounded by the second metal block 60b. The heat of reaction conducted to the coolant circulation unit 50 is absorbed by the coolant circulated in the coolant circulation unit 50.
該第一金屬塊60a並不限於特定態樣,只要其包圍該第三通道30。具體而言,其可由具有高度熱傳導性的金屬材料製成。該第二金屬塊60b並不限於特定態樣,只要其包圍該冷卻劑循環單元50。具體而言,其可由具有高度熱傳導性的金屬材料製成。 The first metal block 60a is not limited to a specific aspect as long as it surrounds the third channel 30. Specifically, it can be made of a metal material having high thermal conductivity. The second metal block 60b is not limited to a specific aspect as long as it surrounds the coolant circulation unit 50. Specifically, it can be made of a metal material having high thermal conductivity.
在一示例性實施例中,該第一金屬塊60a與第二金屬塊60b可具有矩形之形狀。若該第一金屬塊60a與第二金屬塊60b具有較大之接觸區域,反應熱可較佳地由該第三通道30傳導至該冷卻劑循環單元50。 In an exemplary embodiment, the first metal block 60a and the second metal block 60b may have a rectangular shape. If the first metal block 60a and the second metal block 60b have a larger contact area, heat of reaction may preferably be conducted from the third channel 30 to the coolant circulation unit 50.
步驟一:起始原料鹼性水溶液與酸性水溶液之注入 首先,包含二氧化鍺(GeO 2)與一鹼金屬氫化物之一起始原料鹼性水溶液,以及一酸性水溶液分別被注入進一第一通道10與一第二通道20。 Step 1: Injecting of the basic raw material aqueous solution and the acidic aqueous solution First, an alkaline aqueous solution containing a starting material of cerium oxide (GeO 2 ) and an alkali metal hydride, and an acidic aqueous solution are injected into a first passage 10 and a second passage 20, respectively.
該注入進第一通道10之起始原料鹼性水溶液,可藉由二氧化鍺(GeO 2)與一鹼金屬氫化物及一鹼性水溶液混合製備。該鹼金屬氫化物可為NaBH 4。該起始原料鹼性水溶液,如美國專利第4,668,502號中所描述,可藉由添加一鹼金屬氫化物粉末至二氧化鍺(GeO 2)之金屬氫氧化物水溶液中製備,或藉由預先製備一預定濃度之鹼性水溶液以及隨後於其中加入二氧化鍺粉末與鹼金屬氫化物製備,但本發明並不限於上述態樣。在本發明所使用之起始原料鹼性水溶液中,二氧化鍺之濃度具體而言可不高於0.5mol/L,更具體而言為0.3mol/L。每1mol之二氧化鍺,可包含2或更多當量的該金屬氫氧化物,以及每1mol之二氧化鍺,可包含4或更多mol的該鹼金屬氫化物。在上述範圍之外,可能降低二氧化鍺的轉換比率,以及因而降低單鍺烷氣體生產之經濟效益。該鹼性水溶液可為一鹼金屬水溶液或一鹼土金屬水溶液,具體而言為一NaOH水溶液或一KOH水溶液。若使用一NaOH水溶液以及若使用NaBH 4作為一鹼金屬氫化物製備該起始原料鹼性水溶液,因為NaBH 4被穩定化氫氣不會被產生。 The alkaline aqueous solution of the starting material injected into the first passage 10 can be prepared by mixing cerium oxide (GeO 2 ) with an alkali metal hydride and an alkaline aqueous solution. The alkali metal hydride can be NaBH 4 . The starting material alkaline aqueous solution, as described in U.S. Patent No. 4,668,502, may be prepared by adding an alkali metal hydride powder to a metal hydroxide aqueous solution of cerium oxide (GeO 2 ) or by pre-preparation. A predetermined concentration of an aqueous alkaline solution and subsequent addition of cerium oxide powder and an alkali metal hydride are prepared, but the present invention is not limited to the above. In the alkaline aqueous solution of the starting material used in the present invention, the concentration of cerium oxide may specifically be not more than 0.5 mol/L, more specifically 0.3 mol/L. Each 1 mol of cerium oxide may contain 2 or more equivalents of the metal hydroxide, and may contain 4 or more moles of the alkali metal hydride per 1 mol of cerium oxide. Outside of the above range, it is possible to reduce the conversion ratio of cerium oxide and thus the economic efficiency of monodecane gas production. The alkaline aqueous solution may be an aqueous alkali metal solution or an alkaline earth metal aqueous solution, specifically an aqueous NaOH solution or an aqueous KOH solution. If an aqueous solution of NaOH is used and if a basic aqueous solution of the starting material is prepared using NaBH 4 as an alkali metal hydride, hydrogen is not produced because NaBH 4 is stabilized.
該注入進第二通道20之酸性水溶液,可藉由選自無機酸(如,硫酸及磷酸等)或有機酸(如,醋酸及丙酸等)之一酸與水混合製備。具體而言,考慮到單鍺烷氣體之純化,可避免揮發酸(如,鹽酸)之使用。該酸性水溶液並不限定於特定濃度。 The acidic aqueous solution injected into the second passage 20 can be prepared by mixing an acid selected from a mineral acid (e.g., sulfuric acid and phosphoric acid) or an organic acid (e.g., acetic acid and propionic acid) with water. Specifically, the use of a volatile acid such as hydrochloric acid can be avoided in consideration of purification of a monodecane gas. The acidic aqueous solution is not limited to a specific concentration.
該起始原料鹼性水溶液與該酸性水溶液之注入速率 可為每分鐘數十毫升。該注入速率,可依據該裝置之尺寸以及鍺烷氣體所需之生產量變換。 The injection rate of the alkaline aqueous solution of the starting material and the acidic aqueous solution It can be tens of milliliters per minute. The injection rate can be varied depending on the size of the device and the throughput required for the decane gas.
該起始原料鹼性水溶液與該酸性水溶液,可使用任何能夠持續注入該起始原料鹼性水溶液與該酸性水溶液之裝置,注入該第一通道10與該第二通道20,並不限定於特定態樣。具體而言,可使用一計量泵等。 The alkaline aqueous solution of the starting material and the acidic aqueous solution may be injected into the first passage 10 and the second passage 20 by using any means capable of continuously injecting the alkaline aqueous solution of the starting material and the acidic aqueous solution, and is not limited to a specific one. Aspect. Specifically, a metering pump or the like can be used.
步驟二 Step two
該分別注入第一通道10與第二通道20之起始原料鹼性水溶液與酸性水溶液,經由該通道被傳輸至連接該第一通道10之一端與該第二通道20之一端的一第三通道30。在該第三通道30中,該傳輸之起始原料鹼性水溶液與酸性水溶液被混合,以及鍺烷氣體之產生發生於其彼此接觸之界面。 The raw material alkaline aqueous solution and the acidic aqueous solution respectively injected into the first channel 10 and the second channel 20 are respectively transmitted through the channel to a third channel connecting one end of the first channel 10 and one end of the second channel 20 30. In the third passage 30, the transported starting material alkaline aqueous solution is mixed with the acidic aqueous solution, and the generation of decane gas occurs at the interface where they contact each other.
具體而言,該反應發生於其中之第三通道30可為一微通道。就一微通道來說,該第三通道30可促進鍺烷氣體之產生,以及極大化控制伴隨而生之反應熱所造成之溫度上升的效果。這是因為,鍺烷氣體之產生只發生在該起始原料鹼性水溶液與該酸性水溶液彼此接觸之界面。也就是說,該二溶液彼此接觸之區域,隨著該溶液減小為液滴尺寸,使得該區域之面積增加且數目增多,使其在微米尺度下更易於混合。 Specifically, the third channel 30 in which the reaction occurs may be a microchannel. In the case of a microchannel, the third channel 30 promotes the production of decane gas and maximizes the effect of controlling the temperature rise caused by the reaction heat generated. This is because the generation of decane gas occurs only at the interface where the starting aqueous alkaline solution and the acidic aqueous solution contact each other. That is, the area where the two solutions contact each other as the solution is reduced to the droplet size, so that the area of the area increases and the number increases, making it easier to mix on the micrometer scale.
該第三通道30可包含一主要通道30a以及構成於該主要通道一側之複數個平行突出的突出部分30b。該複數個突出部分30b可對於該主要通道具有一銳角並且可朝一個方向突出。據此,該分別注入第三通道30之起始原料鹼性水溶液與酸性水溶液,可在主 要通道30a與突出部分30b之間持續地向上與向下移動,以及得以被分離或重組。其結果,該起始原料鹼性水溶液與該酸性水溶液在微米尺度下混合,以及於界面相互反應產生鍺烷氣體。 The third passage 30 may include a main passage 30a and a plurality of parallel protruding projections 30b formed on one side of the main passage. The plurality of protruding portions 30b may have an acute angle to the main passage and may protrude in one direction. According to this, the alkaline aqueous solution and the acidic aqueous solution of the starting material respectively injected into the third channel 30 can be respectively in the main The passage 30a and the projection 30b are continuously moved upward and downward, and are separated or recombined. As a result, the starting aqueous alkaline solution is mixed with the acidic aqueous solution at a micrometer scale, and the interface is mutually reacted to produce a decane gas.
反應熱在鍺烷氣體生成時產生。由於該反應熱,該第三通道30中之溫度可能快速的上升。為解決此一問題,一冷卻劑循環單元50鄰近該第三通道30配置,吸收該反應發生時之反應熱。 The heat of reaction is generated when decane gas is generated. Due to the heat of reaction, the temperature in the third passage 30 may rise rapidly. To solve this problem, a coolant circulation unit 50 is disposed adjacent to the third passage 30 to absorb the heat of reaction when the reaction occurs.
在一示例性實施例中,鍺烷氣體於該第三通道30中產生,以及該於鍺烷氣體生成時所產生之反應熱被傳導至包圍該第三通道30之一第一金屬塊60a。該第一金屬塊60a傳導該反應熱至與第一金屬塊60a接觸之一第二金屬塊60b。該傳導至該第二金屬塊60b之反應熱被傳導至該被第二金屬塊60b包圍之冷卻劑循環單元50。該傳導至冷卻劑循環單元50之反應熱被於冷卻劑循環單元50中循環的一冷卻劑吸收。該反應熱之吸收,可藉由調控供應至該冷卻劑循環單元之冷卻劑的溫度與流速加以控制。若該起始原料鹼性水溶液與該酸性水溶液之注入量為了增加鍺烷氣體之產生而增加,可藉由降低該冷卻劑之溫度或藉由增加該冷卻劑之流量來維持該第三通道30內部反應溫度的恆定。 In an exemplary embodiment, decane gas is generated in the third passage 30, and the heat of reaction generated when the decane gas is generated is conducted to the first metal block 60a surrounding one of the third passages 30. The first metal block 60a conducts the heat of reaction to one of the second metal blocks 60b in contact with the first metal block 60a. The heat of reaction conducted to the second metal block 60b is conducted to the coolant circulation unit 50 surrounded by the second metal block 60b. The heat of reaction conducted to the coolant circulation unit 50 is absorbed by a coolant circulating in the coolant circulation unit 50. The absorption of the heat of the reaction can be controlled by regulating the temperature and flow rate of the coolant supplied to the coolant circulation unit. If the amount of the alkaline aqueous solution of the starting material and the acidic aqueous solution is increased in order to increase the generation of the decane gas, the third passage 30 may be maintained by lowering the temperature of the coolant or by increasing the flow rate of the coolant. The internal reaction temperature is constant.
該第三通道30中之溫度可藉由調控至少選自冷卻劑之流量、冷卻劑之溫度以及該起始原料鹼性水溶液或該酸性水溶液之流速加以控制。該第三通道中之溫度具體而言可維持在50℃或更低的溫度,更具體而言為0-50℃。若溫度較高,該起始原料鹼性水溶液與該酸性水溶液反應之結果,可能促進較高之鍺烷而非單鍺烷之生成,因此對於單鍺烷氣體之產率有負面的影響。 The temperature in the third passage 30 can be controlled by adjusting the flow rate selected from at least the coolant, the temperature of the coolant, and the flow rate of the starting aqueous alkaline solution or the acidic aqueous solution. The temperature in the third passage can be specifically maintained at a temperature of 50 ° C or lower, more specifically 0-50 ° C. If the temperature is high, the reaction of the basic aqueous solution of the starting material with the acidic aqueous solution may promote the formation of higher decane rather than monodecane, and thus has a negative effect on the yield of the monodecane gas.
在一示例性實施例中,該第三通道30之數量可至少為一,該至少為一之第三通道30可被平行的連接,以及該起始原料鹼性水溶液與該酸性水溶液可被分別注入該至少為一之第三通道30,以便於該至少為一之第三通道30之中產生單鍺烷氣體。若該第三通道30被平行的連接,可以工業規模生產大量之單鍺烷氣體。 In an exemplary embodiment, the number of the third channels 30 may be at least one, the at least one third channel 30 may be connected in parallel, and the starting material alkaline aqueous solution and the acidic aqueous solution may be respectively separated. The at least one third channel 30 is implanted to generate monodecane gas in the at least one third channel 30. If the third passages 30 are connected in parallel, a large amount of monodecane gas can be produced on an industrial scale.
步驟三 Step three
由該反應產生之單鍺烷氣體與反應溶液,透過連接第三通道30之一端的一排放出口40排放出該第三通道30。該排放之單鍺烷氣體被分別於該反應溶液收集。透過上述之步驟,單鍺烷氣體之生產可具有90%或更高的高產率。 The monodecane gas and the reaction solution produced by the reaction are discharged through the discharge port 40 connected to one end of the third passage 30 to discharge the third passage 30. The discharged monodecane gas is separately collected in the reaction solution. Through the above steps, the production of monodecane gas can have a high yield of 90% or higher.
當使用現行的批次反應器或連續反應器,即便冷卻劑於包圍該反應器之冷卻套中循環,仍難以控制反應器內部因鍺烷氣體生成所產生之反應熱所造成之溫度上升。 When a current batch reactor or a continuous reactor is used, even if the coolant circulates in the cooling jacket surrounding the reactor, it is difficult to control the temperature rise caused by the heat of reaction generated by the formation of decane gas inside the reactor.
然而,根據本發明之包含一微結構通道之反應器之優點,不僅在於更容易混合與反應該起始原料鹼性水溶液或該酸性水溶液,亦在於因極大化的冷卻效果該反應器之溫度可被輕易地維持在0-50℃。因此,大量的單鍺烷氣體可被高產率的生產。 However, the advantage of the reactor comprising a microstructured channel according to the present invention is not only that it is easier to mix and react the starting aqueous alkaline solution or the acidic aqueous solution, but also because the temperature of the reactor can be maximized due to the cooling effect. It is easily maintained at 0-50 °C. Therefore, a large amount of monodecane gas can be produced in a high yield.
在下文中,將透過實施例詳細描述本發明。然而,下列之實施例僅為說明之用途,且所屬技術領域具有通常知識者可明確的瞭解,本發明之範疇並不限定於該等實施例。 Hereinafter, the present invention will be described in detail through examples. However, the following examples are for illustrative purposes only, and those skilled in the art can clearly understand the scope of the invention, and the scope of the invention is not limited to the embodiments.
在20℃下,將75g之濃硫酸(96%,H 2SO 4)溶於500mL之蒸餾水中,製備一酸性水溶液。 An acidic aqueous solution was prepared by dissolving 75 g of concentrated sulfuric acid (96%, H 2 SO 4 ) in 500 mL of distilled water at 20 °C.
在20℃下,將2.28mL之50% NaOH水溶液溶於 250mL之蒸餾水中,接著依序將3.4g之二氧化鍺(GeO 2)及7.4g之NaBH 4溶於上述所得之溶液中,製備一起始原料鹼性水溶液。 Dissolve 2.28 mL of 50% NaOH in 20 ° C In 250 mL of distilled water, 3.4 g of cerium oxide (GeO 2 ) and 7.4 g of NaBH 4 were sequentially dissolved in the above-obtained solution to prepare a starting aqueous alkaline solution.
將該起始原料鹼性水溶液以8mL/min之速率,注入根據本發明之一示例性實施例之鍺烷氣體製備裝置(見第2a圖)中之一第一通道10中。在此同時,將該酸性水溶液以16mL/min之速率,注入一第二通道20中。上述之溶液係使用一計量泵注入。使用一裝置測量當鍺烷氣體產生時溫度之上升。測量透過連接於一第三通道30之一排放出口40所排放之反應溶液的溫度。 The starting aqueous alkaline solution was injected into the first passage 10 in a decane gas producing apparatus (see Fig. 2a) according to an exemplary embodiment of the present invention at a rate of 8 mL/min. At the same time, the acidic aqueous solution was injected into a second passage 20 at a rate of 16 mL/min. The above solution was injected using a metering pump. A device is used to measure the rise in temperature as the decane gas is produced. The temperature of the reaction solution discharged through the discharge outlet 40 connected to one of the third passages 30 is measured.
當第三通道30之溫度維持恆定時,開始該鍺烷氣體製備裝置之冷卻劑循環單元中,以乙二醇作為冷卻劑之循環。該第三通道30中之溫度維持在約38℃,於此溫度開始乙二醇之循環。該乙二醇以15℃、120mL/min之流速供應。當開始該冷卻劑之循環,該第三通道30之溫度快速下降,維持於約23℃。 When the temperature of the third passage 30 is maintained constant, the circulation of the refrigerant circulation unit of the decane gas producing apparatus with ethylene glycol as a coolant is started. The temperature in the third passage 30 is maintained at about 38 ° C at which temperature the cycle of ethylene glycol begins. The ethylene glycol was supplied at a flow rate of 15 ° C and 120 mL / min. When the circulation of the coolant is started, the temperature of the third passage 30 drops rapidly and is maintained at about 23 °C.
該起始原料鹼性水溶液與該酸性水溶液之流速增加為2、3及4倍,其他條件控制維持與實施例1相同。 The flow rate of the alkaline aqueous solution of the starting material and the acidic aqueous solution was increased by 2, 3 and 4 times, and the other conditions were maintained as in Example 1.
在實施例2中,該第三通道30之溫度維持在42℃。當乙二醇以5℃供應,該第三通道30之溫度快速下降,維持於約28℃(見第4圖)。 In Example 2, the temperature of the third passage 30 was maintained at 42 °C. When ethylene glycol is supplied at 5 ° C, the temperature of the third passage 30 drops rapidly and is maintained at about 28 ° C (see Figure 4).
在實施例3中,該第三通道30之溫度維持在43℃。當乙二醇以-5℃供應,該第三通道30之溫度快速下降,維持於約30℃(見第4圖)。 In Example 3, the temperature of the third passage 30 was maintained at 43 °C. When ethylene glycol is supplied at -5 ° C, the temperature of the third passage 30 drops rapidly and is maintained at about 30 ° C (see Figure 4).
在實施例4中,該第三通道30之溫度維持在43℃。當乙二醇以-10℃供應,該第三通道30之溫度快速下降,維持於約32 ℃(見第4圖)。 In Example 4, the temperature of the third passage 30 was maintained at 43 °C. When ethylene glycol is supplied at -10 ° C, the temperature of the third passage 30 drops rapidly, maintaining at about 32 °C (see Figure 4).
一起始原料鹼性水溶液與一酸性水溶液以如同實施例1之方式製備。 A starting material alkaline aqueous solution and an acidic aqueous solution were prepared in the same manner as in Example 1.
使用一計量泵以相同於實施例4流速,將該起始原料鹼性水溶液與該酸性水溶液注入一1公升玻璃(glass)反應器中。 The starting aqueous alkaline solution and the acidic aqueous solution were injected into a 1 liter glass reactor using a metering pump at the same flow rate as in Example 4.
當該1公升玻璃反應器之溫度達到43℃,以-10℃、250mL/min之流速循環乙二醇(冷卻劑),(見第五圖)。 When the temperature of the 1 liter glass reactor reached 43 ° C, ethylene glycol (coolant) was circulated at a flow rate of -10 ° C and 250 mL / min (see Figure 5).
對照實施例4與比較實施例1之結果,當使用本發明之鍺烷氣體製備裝置(實施例4),相較於使用現行反應器(比較實施例1),顯著改善該冷卻劑乙二醇之冷卻效果。歸功於該卓越的冷卻效果,更容易藉由控制大量生產鍺烷氣體時所產生之反應熱,維持適合單鍺烷氣體製備的溫度(即,0-50℃),(見第5圖)。 Comparing the results of Comparative Example 4 with Comparative Example 1, when the decane gas producing apparatus of the present invention (Example 4) was used, the coolant ethylene glycol was remarkably improved as compared with the use of the current reactor (Comparative Example 1). Cooling effect. Thanks to this excellent cooling effect, it is easier to maintain the temperature suitable for the preparation of monodecane gas (ie, 0-50 ° C) by controlling the heat of reaction generated when mass producing decane gas (see Figure 5).
據此,可見該根據本發明之鍺烷氣體製備裝置與單鍺烷氣體製備方法,其優點不僅在於混合與反應該反應物,亦在於控制因反應熱而上升之反應溫度。藉此,大量的單鍺烷氣體可被高產率的生產。 Accordingly, it can be seen that the decane gas producing apparatus and the monodecane gas producing method according to the present invention have an advantage not only in mixing and reacting the reactant but also in controlling the reaction temperature which rises due to the heat of reaction. Thereby, a large amount of monodecane gas can be produced in a high yield.
儘管該等示例性實施例已被揭示與描述,應瞭解所屬技術領域具有通常知識者,可對於其形式與細節進行多種變換,而不背離本發明申請專利範圍所界定之精神與範疇。 While the present invention has been shown and described, it will be understood that
10‧‧‧第一通道 10‧‧‧First Passage
20‧‧‧第二通道 20‧‧‧second channel
30‧‧‧第三通道 30‧‧‧ third channel
40‧‧‧排放出口 40‧‧‧Exhaust export
50‧‧‧冷卻劑循環單元 50‧‧‧ coolant circulation unit
55a‧‧‧冷卻劑入口 55a‧‧‧ coolant inlet
55b‧‧‧冷卻劑排放出口 55b‧‧‧ coolant discharge
60a‧‧‧第一金屬塊 60a‧‧‧First metal block
60b‧‧‧第二金屬塊 60b‧‧‧Second metal block
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KR20120090756A KR101250172B1 (en) | 2012-08-20 | 2012-08-20 | Method for preparing mono germane gas in high yield |
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US (1) | US9586820B2 (en) |
JP (1) | JP5952969B2 (en) |
KR (1) | KR101250172B1 (en) |
CN (1) | CN104619644B (en) |
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CN106467290A (en) * | 2015-08-20 | 2017-03-01 | 贺孝鸣 | A kind of electromotive force that adjusts manipulates production method and device prepared by germane |
CN109205660A (en) * | 2018-11-22 | 2019-01-15 | 衡阳恒荣高纯半导体材料有限公司 | A kind of method of purification of germanium dioxide |
US11091374B1 (en) * | 2019-09-28 | 2021-08-17 | Ge Solartech, LLC | Method to produce high purity germane from germanium dioxide or impure germanium compounds |
CN111777040A (en) * | 2020-07-31 | 2020-10-16 | 江西华特电子化学品有限公司 | Purification production process and production system of high-purity germane |
CN112408327B (en) * | 2020-12-18 | 2024-07-09 | 天津中科拓新科技有限公司 | Method and device for preparing electronic-grade germane and co-producing electronic-grade tetrafluorogermane |
KR102538855B1 (en) * | 2021-05-21 | 2023-06-02 | 주식회사 솔 머티리얼즈 | Apparatus and method for manufacturing germane gas |
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US4668502A (en) * | 1986-01-13 | 1987-05-26 | Voltaix, Inc. | Method of synthesis of gaseous germane |
US6388317B1 (en) * | 2000-09-25 | 2002-05-14 | Lockheed Martin Corporation | Solid-state chip cooling by use of microchannel coolant flow |
CN101723326A (en) * | 2009-12-18 | 2010-06-09 | 浙江理工大学 | Preparation method of germane |
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JP3865455B2 (en) * | 1997-04-18 | 2007-01-10 | 三井化学株式会社 | Method for producing germane |
JP2000302411A (en) * | 1999-04-21 | 2000-10-31 | Mitsui Chemicals Inc | Production of monogermane |
KR20100022454A (en) * | 2007-03-30 | 2010-03-02 | 레브 리뉴어블 에너지 벤쳐스 인코포레이티드 | Catalytic hydrogenation |
US7591985B2 (en) * | 2007-05-31 | 2009-09-22 | Metaloid Precursors, Inc. | Method for purifying germanium hydrides |
US20100183500A1 (en) * | 2009-01-17 | 2010-07-22 | Henry Lee | Germane gas production from germanium byproducts or impure germanium compounds |
DE102009056731A1 (en) * | 2009-12-04 | 2011-06-09 | Rev Renewable Energy Ventures, Inc. | Halogenated polysilanes and polygermanes |
-
2012
- 2012-08-20 KR KR20120090756A patent/KR101250172B1/en active IP Right Grant
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2013
- 2013-08-16 WO PCT/KR2013/007402 patent/WO2014030885A1/en active Application Filing
- 2013-08-16 TW TW102129464A patent/TW201425227A/en unknown
- 2013-08-20 CN CN201380043627.9A patent/CN104619644B/en active Active
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- 2013-08-20 JP JP2015527396A patent/JP5952969B2/en active Active
- 2013-08-20 WO PCT/KR2013/007465 patent/WO2014030909A1/en active Application Filing
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Patent Citations (3)
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US4668502A (en) * | 1986-01-13 | 1987-05-26 | Voltaix, Inc. | Method of synthesis of gaseous germane |
US6388317B1 (en) * | 2000-09-25 | 2002-05-14 | Lockheed Martin Corporation | Solid-state chip cooling by use of microchannel coolant flow |
CN101723326A (en) * | 2009-12-18 | 2010-06-09 | 浙江理工大学 | Preparation method of germane |
Also Published As
Publication number | Publication date |
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CN104619644B (en) | 2016-12-14 |
JP2015526378A (en) | 2015-09-10 |
WO2014030909A1 (en) | 2014-02-27 |
US20150175418A1 (en) | 2015-06-25 |
TW201425232A (en) | 2014-07-01 |
US9586820B2 (en) | 2017-03-07 |
CN104619644A (en) | 2015-05-13 |
TW201425227A (en) | 2014-07-01 |
KR101250172B1 (en) | 2013-04-05 |
WO2014030885A1 (en) | 2014-02-27 |
JP5952969B2 (en) | 2016-07-13 |
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